Thioltriazine salt compounds



United States Patent "ice 3,267,098 THIOLTRIAZINE SALT COMPOUNDS Richard P. Cope, Jr., Wilkinsburg, Pa., assignor, by mesne assignments, to Cowles Chemical Company, Shaker Heights, Ohio, a corporation of Ohio No Drawing. Filed Feb. 25, 1963, Ser. No. 260,896 Claims. (Cl. 260-248) This invention relates to the water soluble salts produced by the reaction of certain substituted and unsubstituted thioltriazines with certain substituted and unsubstituted primary and secondary amines.

Heretofore, numerous compounds have been employed as additives to electroplating baths. The problems of obtaining satisfactory electrodeposits are manifold. Deposits of metal are frequently required to possess one or more properties such as brightness, ductility, refined grain, smoothness and attractive color. In the electroplating process, current density ranges are important. Compounds which improve one or more of these properties of the electrodeposited metal or which improve the plating process are added to the electrolyte solutions either singly or in combination with other additives.

To be efiicacious, the additive compounds must generally be soluble in the plating solutions or electrolytes which are typically aqueous solutions containing the metal to be deposited in ionic form as well as the soluble additive compound. Although the additive compound may be somewhat more soluble in the plating electrolyte than in water, it may be generally stated that such additive compounds should be water soluble. It should be recognized, however, that the solubility, especially the water solubility of the additive compounds may be of a relatively low order of magnitude since as little as 0.0005 02. per gallon of electrolyte of some additives will produce observable improvements in the deposited metal.

Accordingly, it is an object of this invention to provide novel Water soluble thioltriazine based salt compounds which may be employed as additives for electroplating baths.

Another object of this invention is to provide new water soluble salts derived from the reaction of certain substiuted and unsubstituted thioltriazines with certain substituted and unsubstituted primary and secondary amines.

Yet another object of this invention is to improve the solubility of certain triazine compounds by reacting them with amines.

Other and further objects of this invention will, in part, be obvious and will, in part, appear hereinafter.

Briefly, this invention comprises reacting thioltriazines with primary and secondary amines to produce Water soluble salt compounds. The primary and secondary amines react with the thiol radical of the thiol substituted triazine. The amines may be aliphatic, alicyclic or heterocyclic, substituted with such radicals as --NH Cl, OH and SO Na. The thioltriazin'es should have either two or three thiol groups. The dithioltriazines may be further substituted with radicals such as methyl, amino or hydroxyl radicals. The compounds produced by this reaction will be water soluble salts having utility as additives for electroplating baths.

In accordance with this invention, the compounds are prepared by reacting (A) at least one compound having the formula:

wherein R is a group selected from the group consisting 3,267,098 Patented August 16, 1966 of hydrogen, thiol, amino and hydroxyl radicals with (B) at least one compound having the formula:

Rs wherein R is selected from the group consisting of (1) hydrogen, (2) substituted and unsubstituted aliphatic groups containing not more than four carbon atoms in which the substituents are selected from the group consisting of NH -Cl, OH and SO ;Na, (3) substituted and unsubstituted alicyclic groups containing from 4 to 6 carbon atoms in which the substituents are selected from the group consisting of -NH -Cl, OH and -SO Na and R is selected from the heretofore described groups (2) and (3).

Examples of suitable compounds described by the formula (A) hereinabove, referred to hereinafter as thioltriazine compounds for convenience, include clithioammelide, dithiocyanuric acid, Z-methyl-s-triazine-4-6-dithiol, 2,4-s-triazinedithiol and trithiocyanuric acid.

Examples of compounds which may be employed in the reaction with the described thioltriazine compounds include methylolamine, 2-chloroethylamine, 1,4-diaminobutane, ethylamine, the sodium salt of 3-amino-n-proplysulfonic acid, methylethylamine, (aminoethyl) ethylamine, diethylolamine, methylhydroxymethylamine, di(chloropropyl) amine, aniline, chloroaniline, p-aminoaniline, 3- hydroxycyclopentylamine, 3 aminobenzenesodiumsulfonate, diphenylamine, 2 hydroxycyclobutenyl phenyl amine, methyl phenyl amine, 3hydroxy-ethylaminobenzene sulfonic acid sodium salt, di(p-aminophenyl)amine, chloromethylaniline, diethylenetriamine, Z-aminothiazole, pyridine, pyridine-3-sulfonic acid salt, Z-methylaminopyrrole, 3-aminopyridine, 2,4-dihydroxypyridine, 2-amino- 5-chlorofuran, 3,5-dichloropyridine, and guanidine. It is apparent that these compounds are described by the formula (B) hereinabove. For convenience, these compounds will be referred to hereinafter as the amino com pounds.

The described amino compounds are sutficiently strong bases so that they will react with the hydrogen of the thiol radical of the thioltriazine compound to form a salt therewith. It is apparent that the described thioltriazine compounds may contain two or three thiol groups. One to three moles of the amino compounds may be employed to react with the thiol groups.

It is to be understood that dithioammelide exists as an intramolecular salt. The amine group of the dithioammelide being basic enough to react with a thiol group on another molecule of dithioammelide. The formula outlined hereinabove in the case of dithioammelide then should be considered to 'be an empirical formula, the intramolecular salt being a dimer or polymer of this formula. Obviously in this intramolecular salt only one thiol group of the dithioammelide is aavilable for further reaction with an amine.

Obviously, in products resulting from the reaction of amines with these thioltriazines all of the thiol groups are not necessarily reacted. If, for example, only one mole of an amine is reacted with trithiocyanuric acid it is apparent that all of the thiol groups would not be reacted.

While other mediums may be employed, either water or lower alkyl alcohols having up to 4 carbon atoms are preferred as the solvent or reaction medium. Alkylolamines are the preferred amino compounds because they produce salt compounds which are among the most water soluble.

The resulting salt compounds are more soluble than the s-triazines in plating electrolytes and, as noted here inabove, may be advantageously employed as additives to improve the properties of the deposited metals. The salt compounds, as for example that resulting from the reaction of trithiocyanuric acid and monoethanolamine, act as a grain refiner for copper deposited from an acid bath. Particularly effective advantages attend the use of these reaction products in other plating baths and processes, as for example those disclosed and claimed in US. application Serial No. 260,823, filed February 25, 1963, which is assigned to the assignee of this invention.

The following specific examples are set forth to illustrate the preparation of the novel compounds in accordance with the present invention.

Example A About 1 mole of trithiocyanuric acid is slurried in a minimum quantity of n-butyl alcohol and heated to refluxing temperature. Dimethylamine is slowly bubbled into the refluxing mixture for 5 hours. The solid triazine will go into solution. The solution is then filtered while hot to remove a small amount of decomposed solid material from the solution. The reaction mixture is then cooled to C. causing the tri(methylam-monium) salt to crystallize. The solid is filtered from the liquid on a Biichner funnel and air dried. About 243 grams of a pale yellow material is recovered.

Example B About 0.1 mole of dithioammelide was mixed with 0.11 mole of 2-aminoethanol and 600 ml. of ethanol. The reaction mixture was heated to boiling, filtered while hot to remove a slight amount of decomposed material and cooled to room temperature. On cooling, yellow crystals were precipitated. The reaction mixture was filtered on a Bii-chner funnel and the precipitate was washed with 50 ml. of cold alcohol and air dried. The solid was dried in a vacuum desiccator. A 70% yield of the 2-hydroxyethylammonium salt was obtained. This compound melted with decomposition starting at 197 C.

Example C About 0.5 mole of s-triazine-2,4-dithiol was refluxed in an excess of freshly distilled n-butylamine under a blanket of nitrogen gas for 2 hours. The reaction mixture was then cooled to 0-5 C. in an ice bath and slowly neutralized with a 5% HCl solution. A yellow precipitate of the dibutylammonium salt resulted.

Example D About 0.1 mole of Z-methyl-s-triazine 4,6-dithiol was slurried in 500 ml. of water. About 0.1 mole of 2-aminothiazole and 0.11 mole of 3-aminopyridine were added. The reaction mixture was heated to reflux temperatures with stirring. The aminothiazole melted and formed yellow oily droplets in the solution at reflux. The reaction mixture was refluxed for 7 hours. It was then cooled to 10 C. and filtered. The recovered solid was recrystallized from methanol. A yield of the mixed salt was obtained.

Example E About 0.1 mole of dithiocy-anuric acid, 600 ml. of water and 0.22 mole of sodium amino'benzenesulfonate were refluxed for 2 hours. The solution of the reaction product was then diluted to 2 liters with water. This water solution was used as an additive for plating baths and produced an improved deposit.

Example F About 1 mole of trithiocyanuric acid was slurried in 2 liters of a 50:50 ethanolzwater (by volume) solution. About two moles of methylethanol amine were added and the reaction mixture was refluxed for 1 hour. The reaction mixture was then filtered while hot and cooled to 10 C., a yellow solid precipitated and was filtered from the solution. The filtered solution was then evaporated down to about 500 ml. by boiling, filtered while hot and again cooled to 10 C. A second crop of slightly darker yellow crystals was obtained. The total yield of the combined precipitated amine salt was approximately 60%.

Example G About 0.1 mole of dithiocyanuric acid was slurried in 400 ml. of a 60:40 alcoholzbenzene solution. About 0.1 mole of methylchloroaniline was added. The reaction mixture was heated while stirring to reflux. The solid material dissolved after a short reflux time. The solution was then cooled. A greenish-brown precipitate of the anilinium salt precipitated.

While the present invention has been described with reference to preferred embodiments thereof, it will be understood, of course, that certain changes, substitutions, modifications and the like may be made therein without departing from its true scope.

I claim as my invention:

1. A water soluble amine salt of a thiolt-riazine compound suitable for use as an additive to electroplating baths produced by admixing and heating (A) a thioltriazine compound having the formula:

wherein R is selected from the group consisting of hydrogen, thiol, amino and hydroxyl groups with (B) a compound having the formula:

wherein R is selected from the group consisting of ('1) hydrogen, (2) unsubstituted aliphatic groups containing not more than four carbon atoms and substituted aliphatic groups containing not more than four carbon atoms in which the substituents are selected from the groups consisting of NH Cl, OH and SO Na and (3) unsubstituted alicyclic groups containing from 4 to 6 carbon atoms and substituted alicyclic groups containing from 4' to 6 carbon atoms in which the substituents are selected from the groups consisting of NH Cl, OH and SO Na and R is selected from the heretofore described groups (2) and (3).

2. A water soluble amine salt of a thioltriazine compound suitable for use as an additive to electroplating baths produced by admixing and heating (A) a thioltriazine compound selected from the group consisting of dithiocyanuric acid, dithioammelide, 2-methyl-s-triazine-4- 6-dithiol, 2,4-s-triazinedithiol and trit-hiocyanuric acid with (B) a compound selected from the group consisting of methylolamine, 2-aminoethano1, 2-chloroethylamine, 1,4- diaminobutane, ethylamine, the sodium salt of 3-aminon-propylsulfonic acid, methylethylamine, (aminoethyl) ethylamine, diethylolamine, methylhydroxymethylamine, di(chloropropyl) amine, aniline, chloroaniline, p-aminoaniline, 3hydroxycyclopentylamine, 3 ami-no'benzenesodiumsulfonate, diphenylamine, 2 hydroxycyclobutenyl phenylamine, methylphenylamine, 3-hydroxyethylaminobenzene sulfonic acid sodium salt, di(p-aminophenyl) amine, chloromethylaniline, diethylenet-riamine, 2-aminothiazole, pyridine, pyridine-3-sulfonic acid salt, 2-methylaminopyrrole, B-aminopyridine, 2,4-dihydroxypyridine, 2- amino-S-chlorofuran, and 3,5-dichloropyridine.

3. A method for producing water soluble amine salts of thiolt-riazine compounds which comprises admixing and heating (A) a thioltriazine compound having the formula:

wherein R is selected from the group consisting of hydrogen, thiol, amino and hydroxyl groups with (B) a compound having the formula:

wherein R is selected from the group consisting of (1) hydrogen, (2) unsubstituted aliphatic groups containing not more than four carbon atoms and substituted aliphatic groups containing not more than four carbon atoms in which the substituents are selected from the groups consisting of NH -Cl, OH and SO N-a and (3) unsubstituted alicyclic groups containing from 4 to 6 carbon atoms and substituted alicyclic groups containing from 4 to 6 carbon atoms in which the substituents are selected from the groups consisting of -NH -Cl, OH and SO Na and R is selected from the heretofore described groups (2) and (3).

4. The method of claim 3 in which the molar proportion of (B) to (A) is from about 1 to 1 to about 3 to 1.

5. The method of claim 3 in which the compounds (A) and (B) are reacted in a medium selected from the group consisting of water and an aliphatic alcohol having from 1 to 4 carbons, and mixtures thereof.

6. The method of claim 5 in which said medium is refluxed.

7. A method for producing water soluble amine salts of thioltriazine compounds which comprises admixing and heating (A) a thioltriazine compound selected from the group consisting of dithiocyanuric acid, dithioammelide,

6 2-methyl-s-triazine-4-6-dithiol, 2,4-s-triazinedithiol and trith-iocyanuric acid with (B) a compound selected from the group consisting of methylolamine, Z-aminoethanol, 2-chloroethylamine, 1,4-diaminobutane, ethylamine, the sodium salt of 3-arnino-n-propylsulfonic acid, methylethylamine, (aminoethyl) ethylamine, diethylolamine, methylhydroxyrnethylamine, di(chloropropyl) amine, aniline, chloroaniline, p-aminoaniline, 3-hydroxycyclopentylamine, 3-aminobenzenesodiumsulfonate, diphenylamine, 2 hy droxycyclobutenyl phenylamine, methylphenylamine, 3- hydroxyethylamino benzene sulfonic acid sodium salt, di- (p-aminophenyl) amine, chloromethylaniline, diethylenetriamine, Z-aminothiazole, pyridine, pyridine-3-sulfonic acid salt, Z-methylaminopyrrole, 3-aminopyridine, 2,4-dihydroxypyridine, Z-amino-S-chlorofuran, and 3,5 dichloropyridine.

8. The method of claim 7 in which the molar proportion of (B) to (A) is from about 1 to 1 to about 3 to 1.

9. The method of claim 7 in which the compounds (A) and (B) are reacted in a medium selected from the group consisting of water and an aliphatic alcohol having up to 4 carbons, and mixtures thereof.

10. The method of claim 9 in which said medium is refluxed.

Smolin et al.: s-Triazine and Derivatives, Interscience Pub. Inc., New York (1959), page 110.

WALTER A. MODANCE, Primary Examiner.

NICHOLAS S. RIZZO, MARION W. WESTERN, JOHN M. FORD, Assistant Examiners. 

1. A WATER SOLUBLE AMINE SALT OF A THIOLTRIAZINE COMPOUND SUITABLE FOR USE AS AN ADDITIVE TO ELECTROPLATING BATHS PRODUCED BY ADMIXING THE HEATING (A) A THIOLTRIAZINE COMPOUND HAVING THE FORMULA: 